Bleaching efficiency boosters for bleach and textile detergent compositions

ABSTRACT

Use of amines as bleaching efficiency boosters for textile detergent compositions, where the pK a  of the amines is greater than the pH minus 1, preferably greater than the pH, particularly preferably at least 0.5 greater than the pH of the 1% by weight wash liquor obtained from the textile detergent composition.

This application is a 371 of PCT/EP/01513 filed Mar. 25, 1997.

The invention relates to the use of amines as bleaching efficiencyboosters for textile detergent compositions and to bleach and textiledetergent compositions containing these.

It is known that the bleaching effect of peroxy compounds, peracids andcombinations of peroxy compounds with peracid-liberating activators usedas bleaches can be enhanced by adding bleaching efficiency boosters orbleach catalysts. Examples of metal-free bleach catalysts employed areiminium salts, sulfone imines and N-sulfonyloxaziridines.

EP-B1-0 313 146 gives a general description of the use of secondaryamines of the formula

    (C.sub.6-20 -hydrocarbyl)(C.sub.1-20 -hydrocarbyl)NH

in amounts of 1-10% by weight as additional softening agent in detergentcompositions which contain a bleach and a bleach activator.

EP-A3-0 236 270 gives a general description of aliphatic secondaryamines in amounts of 1-10% by weight as foam generators orsurface-active compounds in conjunction with a specific bleach andbleach activators in speckles.

JP-A-07197097 describes bleach compositions which contain a peroxide ofthe oxygen type, a bleach activator based on acyloxyanilide derivativesand one or more amines, amine salts or quaternary ammonium salts in anamount of at least 1% by weight. In this case, the amines can be thehydrophilic secondary amines diethanolamine, ethanolmethylamine,diisopropanolamine or N-methylaniline. The compositions are used forbleaching dyed textiles, the intention being to avoid loss of color fromthe dyeing.

JP 06248295 describes bleach compositions which have a long shelf lifeand high bleaching efficiency and avoid loss of color from textiles. Thecompositions contain peroxides and a salt consisting of a bleachactivator and an aromatic peracid precursor anion and a quaternaryammonium ion in an amount of at least 0.7% by weight, which can bederived from the hydrophilic secondary amines diethanolamine,diisopropanolamine and dimethylamine.

EP-A-0 173 398 describes detergent compositions which are able to cleanand soften textiles in a washing liquid. It is possible to use asessential textile as softening ingredients a mixture of a long-chainsecondary amine with cellulase. Dilaurylamine, distearylamine andtallow-methylamine are described as usable, in an amount of from 0.5 to15% by weight, preferably 1 to 10% by weight, particularly preferably 2to 5% by weight. The detergent compositions may contain bleaches andbleach activators.

DD 129 565 describes detergent compositions which containantiredeposition agents. It is possible to use as antiredeposition agentricinoleic acid ethanolamide in an amount of 5 parts by weight, inconjunction with sodium borate perhydrate. Also described as suitableare dodecylethanolamine, hexadecylethanolamine and oleic acidethanolamide in an amount of from 1 to 5 parts by weight.

WO 86/07603 describes detergents for low washing temperatures whichcontain as detergency-boosting additive an aliphatic amine compound. Theamido amines listed may be secondary amines, but only tertiary aminesare used in the described detergents, in amounts of more than 1% byweight, with or without the presence of bleaches and bleach activators.

EP-A-0 315 204 describes cyclic secondary amines as quenchers forsinglet oxygen. They are employed in a bleach, in addition to a compoundcontaining active halogen, in an amount of from 0.5 to 40% by weight,preferably 2.0 to 30% by weight. A bleach detergent composition maycontain from 0.1 to 30% by weight of the cyclic hindered secondaryamine, with the amount in the exemplary formulations being at least 5parts by weight.

EP-A3-0 349 153 describes aromatic secondary amines as radicalscavengers for free radicals in liquid hydrogen peroxide compositionswhich contain no activator.

WO 95/33035 describes detergent compositions which containoleoyl-sarcosinate and a surface-active amine. Preferably employed assurface-active amine are primary or tertiary amines. Secondary amineswith two long-chain alkyl radicals are disclosed. The compositions aredescribed as particularly effective for removing fatty or oily soilings.

EP-A1-0 026 529 describes detergent compositions which also act assofteners. They may contain a cationic secondary amine. Examplesindicated are coco-methylamine in an amount of 2% by weight andlaurylbenzylamine.

It is an object of the present invention to provide a bleachingefficiency booster for bleach or textile detergent compositions.

It is another object of the present invention to provide a bleachingefficiency booster which is effective at low temperature.

It is another object of the present invention to provide a bleachingefficiency booster which is suitable for bleaching hydrophobic and/orhydrophilic soilings on textiles.

It is another object of the present invention to provide a bleach ortextile detergent composition containing a bleach and a bleachingefficiency booster and having an improved bleaching effect.

It is another object of the present invention to provide a bleach ortextile detergent composition which shows an improved bleaching effectat low temperature.

It is another object to provide a bleach or textile detergentcomposition which improves the removal of hydrophobic and/or hydrophilicsoilings on textiles.

It is another object to provide a bleach or textile detergentcomposition which comprises a bleaching system and at least one enzyme,with the bleaching system adversely affecting the action of the enzymeonly slightly or not at all.

We have found that these and other objects are achieved by using aminesas bleaching efficiency boosters for textile detergent compositions,where the pKa of the amines is greater than the pH minus 1, preferablygreater than the pH, particularly preferably at least 0.5 greater thanthe pH of the 1% by weight wash liquor obtained from the textiledetergent composition, and by bleach or textile detergent compositionscomprising these bleaching efficiency boosters.

We have found that the claimed amines enhance the bleaching effect ofbleach compositions and textile detergent formulations. In particular,they enhance the bleaching effect of bleach or textile detergentcompositions containing peroxy compounds or peracids, especially forhydrophobic/lipophilic stains on textiles and also for hydrophilic,lipophobic stains.

The bleaching efficiency-boosting effect with the claimed amines makesit possible to use the bleach or textile detergent compositions at lowtemperatures, in particular in the range up to a maximum of 40° C., atwhich bleach compositions often show inadequate effectiveness. Thebleaching efficiency-boosting effect of the amines according to theinvention may moreover be further increased by adding suitable bleachactivators, with or without additional bleach-stabilizing additives.

The use of the amines according to the invention in the bleach ortextile detergent compositions leads to only very little, or no, adverseeffect on the action of enzymes which are likewise present, for exampleproteases. Known bleach systems generally have a marked adverse effecton the activity of enzymes.

There follow first a description of the amines which can be usedaccording to the invention and then the other ingredients in the bleachcompositions and textile detergent compositions according to theinvention which contain bleaching efficiency boosters.

AMINES

The amines or oligo/polyamines used according to the invention asbleaching efficiency boosters have a pK_(a) greater than the pH minus 1,preferably greater than the pH, particularly preferably at least 0.5greater than the pH of the wash liquor obtained from 1% by weight of atextile detergent composition which contains the bleaching efficiencybooster.

In this connection, the pK_(a) means the value for the correspondingacid of the amine, ie. of the protonated amine and is equal to 14-pK_(B)of the amine.

In one embodiment of the invention, the amines used as bleachingefficiency boosters have a pK_(a) above 10, preferably above 10.5,particularly preferably above 10.75. Particularly suitable amines have apK_(a) of from 10.9 to 11.5.

The pH of the wash liquor is, in one embodiment of the invention, from8.5 to 12.0, preferably 9.0 to 11.5, particularly preferably 9.2 to11.0, especially 9.5 to 10.5.

In one embodiment of the invention, the amines are aliphatic amines,that is to say the radicals different from hydrogen atoms are alkylradicals or substituted radicals attached via alkylene radicals, forexample aralkyl radicals.

Examples of amines which can be used are the secondary amines listedbelow.

SECONDARY AMINES

In one embodiment according to the invention, use is made of lowmolecular weight, oligomeric or polymeric compounds which comprisesecondary amino groups --NHR¹, in particular secondary amines of thegeneral formula (I)

    R.sup.1 NH--[(CR.sup.3 R.sup.4).sub.m --NH].sub.n --R.sup.2(I)

where n has an integral value from 0 to 20 and m has an integral valuefrom 2 to 4, the radicals R³ and R⁴ are, independently, C₁₋₃₀ --,preferably C₁₋₁₅ --, hydrocarbyl radicals, and the radicals R¹ and R²are, independently, C₁₋₃₀ --, preferably C₁₋₁₅ --, hydrocarbyl radicalswhich may together form a cyclic radical, or salts thereof as bleachingefficiency boosters for textile detergent compositions.

In one embodiment of the invention, the secondary amine can be mono- orbis-α-branched. A bis-α-branched secondary amine can have the generalformula (II)

    R.sup.4 R.sup.3 HC--HN--CHR.sup.1 R.sup.2                  (II)

where the radicals R¹, R², R³ and R⁴ have, independently of one another,the abovementioned meanings.

The term "hydrocarbyl" used in the description and the claims describesradicals which are based on hydrocarbons with the stated number ofcarbon atoms and which may be pure hydrocarbon radicals but may alsohave substituents. Examples of radicals embraced by the term"hydrocarbyl radicals" are indicated below.

The radicals R¹ and R² can, according to the invention, be C₁₋₃₀ -alkylradicals, preferably C₁₋₂₀ -alkyl radicals, particularly preferablyC₁₋₁₀ -alkyl radicals, which can be straight-chain or branched. Theradicals R¹ and R² can be C₂₋₃₀ -alkenyl radicals, preferably C₂₋₂₀ --,particularly preferably C₂₋₁₀, alkenyl radicals, which can bestraight-chain or branched. The radicals may also be C₅₋₁₈ -cycloalkylradicals which may have branches, it being possible for a ring structureof five to eight carbon atoms to be formed. The radicals R¹ and R² mayfurthermore be C₇₋₁₈ -aralkyl radicals in which an aromatic radical isbonded via an alkyl group to the amine nitrogen atom. The radicals mayalso be C₇₋₁₈ -heteroalkyl radicals or C₆₋₁₈ -aryl radicals or C₃₋₁₈-heteroaryl radicals, with, in the last-mentioned compounds, an aromaticradical being directly linked to the amine nitrogen atom.

The radicals R¹ and R² may furthermore carry one or more, preferablyzero or one, substituents such as hydroxyl groups, C₁₋₄ -alkoxyradicals, amino groups, C₁₋₄ -alkylamino radicals, (di-C₁₋₄ -alkyl)aminoradicals, chlorine atoms, bromine atoms, nitro groups, cyano groups,C₁₋₄ -alkylthio radicals, C₁₋₄ -alkylsulfonyl radicals, carboxyl groups,sulfo groups, carboxy-C₁₋₄ -alkyl radicals, carbamoyl radicals orphenyl, tolyl or benzyl radicals.

The carbon chains in the radicals R¹ and R² may furthermore beinterrupted by oxygen atoms, imino groups, C₁₋₄ -alkylimino radicals,iminocarbonyl radicals, oxycarbonyl radicals or carbonyl radicals.

The radicals R¹ and R² may furthermore together form a cyclic radical sothat, together with the amine nitrogen atom, they provide a cyclicstructure. In this case, the ring of the cyclic radical is preferablyformed from 3 to 13, preferably 5 to 9, in particular 6 to 8, carbonatoms which in turn can be substituted as described above. Preferredcyclic amines are azacyclohexane, azacycloheptane, azacyclooctane,azacyclononane, azacyclodecane, azacycloundecane and azacyclododecane,which may be substituted by C₁₋₈ -alkyl radicals. It is also possiblefor other heteroatoms, such as oxygen or nitrogen atoms, to be presentin the ring structure.

The aromatic, cycloaliphatic or heterocyclic radicals may, just like thealiphatic radicals, be substituted by the abovementioned radicals.

In a preferred embodiment, the radicals R¹ and R₂ are hydrophobicradicals. These radicals are preferably unbranched or branched C₁₋₃₀-alkyl radicals, preferably C₁₋₂₀ -alkyl radicals, particularlypreferably C₁₋₁₀ -alkyl radicals, C₂₋₃₀ -alkenyl radicals, preferablyC₂₋₂₀ -alkenyl radicals, particularly preferably C₂₋₁₀ -alkenylradicals, C₅₋₁₈ -cycloalkyl radicals, C₇₋₁₈ -aralkyl radicals or C₇₋₁₈-heteroaralkyl radicals or C₆₋₁₈ -aryl radicals or C₃₋₁₈ --, preferablyC₆₋₁₈ --, heteroaryl radicals.

The secondary amines are preferably substituted non-symmetrically. Theradicals R¹ and R² are then different from one another, it beingpossible for each of the radicals R¹ and R² to have one of thestructures described above.

In this case, the radical R² is preferably an unbranched or branchedC₁₋₆ -alkyl radical, a C₂₋₆ -alkenyl radical, a C₅₋₈ -cycloalkylradical, a C₇₋₉ -aralkyl radical or C₇₋₉ -heteroaralkyl radical or aC₆₋₁₀ -aryl radical or C₃₋₆ -heteroaryl radical.

The radical R¹ is preferably a C₆₋₁₄ -hydrocarbyl radical whichpreferably has zero or one branch, and the radical R² is a C₁₋₅-hydrocarbyl radical, preferably a methyl radical, and n has the valuezero. The radical R¹ can have, in particular, 7 to 11 carbon atoms.

It is possible in this case for the radicals R¹ and R² in one embodimentof the invention to be further substituted as described above.

Examples of preferred amines are N-hexyl-N-methylamine,N-heptyl-N-methylamine, N-octyl-N-methylamine, N-nonyl-N-methylamine,N-decyl-N-methylamine, N-dodecyl-N-methylamine,N-tridecyl-N-methylamine, N-tetra-decyl-N-methylamine,N-benzyl-N-methylamine, N-phenylethyl-N-methylamine,N-phenylpropyl-N-methylamine, each of which may have linear or branchedhydrocarbon radicals, and the corresponding N-alkyl-N-ethylamines,N-alkyl-N-hydroxyethylamines, N-alkyl-N-propylamines,N-alkyl-N-hydroxypropylamines, N-alkyl-N-isopropylamines,N-alkyl-N-butylamines and N-alkyl-N-isobutylamines and correspondingN-alkyl-N-hydroxyalkylamines in which the methyl radical is replaced byan ethyl, propyl, isopropyl, butyl or isobutyl radical.

Cyclic, Bicyclic and Oligocyclic Amines

As described above, the radicals R¹ and R² on the secondary nitrogenatom may form a cyclic structure. In one embodiment, the secondaryamines are compounds of the general formula (III): ##STR1## where p andq independently have an integral value from 0 to 4, preferably 0, 1 or2,

X is a C₁₋₈ --, preferably C₁₋₄ -alkylene radical which can beinterrupted by O, S, --O--C(O)--, N--R or --NR--C(O)--, where R is a_(C1-8) ; preferably C₁₋₄ -alkyl radical, or

X is a C₂₋₈ --, preferably C₂₋₄ -alkenylene radical,

Y is a C₁₋₈ --, preferably C₁₋₄ -alkyene radical which can beinterrupted by O, S, --O--C(O)--, --NR--C(O)--, or

Y is a C₂₋₈, preferably C₂₋₄ -alkenylene radical, O, S, --O--C(O)--,N--R or --NR--C(O)--, where R is H or a C₁₋₈, preferably C₁₋₄ -alkylradical, or

Y is a C--C single bond ("zero bridge").

X and Y may together form a C--C double bond if p+q has a value of atleast 2. One or more hydrogen atoms bonded to carbon may be replaced byC₁₋₁₀ --, preferably C₁₋₄ --, in particular C₁ -hydrocarbyl radicals.The bridgehead carbon atoms in particular may carry these hydrocarbylradicals.

In one embodiment of the invention, two hydrogen atoms on adjacent ringcarbon atoms at one or more places in the ring can be replaced by a C--Cbond so that a C--C double bond is formed at this place.

In one embodiment of the invention, X and Y are independently C₁₋₈-alkylene radicals with in each case one carbon atom of X and Y beinglinked by a C--C single bond or via a C₁₋₈ --, preferably C₁₋₄ --, inparticular C₁ -alkylene radical or a C₂₋₈ --, preferably C₂₋₄-alkenylene radical.

In one embodiment, X and Y are n-propylene radicals whose central carbonatoms are linked via a methylene group, in which case p=q=0.

X and Y can together form an aromatic ring, preferably an aromatic6-membered ring, as long as p+q has a value of at least 2.

In one embodiment of the invention, p, q, X and Y are chosen so thateach ring present in the molecule has at least 5 ring atoms.

In one embodiment of the invention, the secondary amines of the formula(III) have 5 to 20, preferably 6 to 14, particularly preferably 7 to 12,carbon atoms in the cyclic framework.

In one embodiment of the invention, one or more, preferably 1 to 5, inparticular 1 to 3, hydrogen atoms bonded to carbon in the generalformula (III) are replaced by C₁₋₁₀ --, preferably C₁₋₄ --, inparticular C₁ -hydrocarbyl radicals. These hydrogen atoms can also bereplaced by C₁₋₁₀ --, preferably C₁₋₄ --, in particular C₁ -alkylradicals which may be straight-chain or branched, by C₁₋₁₀ --,preferably C₁₋₄ --, in particular C₁ -alkoxy radicals, C₆₋₁₂ --,preferably C₆₋₈ -aryl radicals or C₆₋₁₂ --, preferably C₆₋₈ -aralkylradicals. Particularly preferred substituents are methyl, ethyl, propyl,i-propyl, n-butyl, i-butyl and tert-butyl radicals, in particular methylradicals.

In one embodiment of the invention, at least one ring in the generalformula (III) is unsaturated. Moreover, in one embodiment of theinvention, the total number of ring carbon atoms is 5 to 20, preferably6 to 14, particularly preferably 7 to 12 carbon atoms.

In one embodiment of the invention, the amines of the formula (III) arebenzo-fused amines with 5 to 20, preferably 6 to 14, particularlypreferably 7 to 12, ring carbon atoms.

The secondary amines of the formula (III) are moreover cyclic, bicyclicor oligocyclic amines.

In one embodiment of the invention, p+q has the value 0 to 4, preferably0 to 2, and X and Y have a total of 3 to 12, preferably 3 to 6, carbonatoms.

In one embodiment of the invention, p and q have the value 0, and eachof the radicals X and Y is independently a C₂₋₆ --, preferably C₂₋₄-alkylene radical. The total of the carbon atoms in the radicals X and Yis moreover preferably 4 to 6. At least one of the radicals X and Y canbe an alkenylene radical, that is to say have a double bond.

In one embodiment of the invention, p+q has the value 2 to 6, preferably2, 3 or 4, and the radicals X and Y together form an aromatic radical,preferably a benzene nucleus.

In one embodiment of the invention, p+q has the value 2 to 7, preferably2, 3 or 4, and X and Y together form a C--C double bond.

In one embodiment of the invention, p has the value 0 and q has thevalue 1.

In one embodiment of the invention, p has the value 1 and q has thevalue 1.

In one embodiment of the invention, p has the value 0 and q has thevalue 1, the radical X is an oxygen or sulfur atom and the radical Y isa C₂₋₆ --, preferably C₂₋₄ --, in particular C₂₋₃ -alkylene or-alkenylene radical which can be interrupted by O, S, --O--C(O)--,--NR--C(O)--, with the above meaning for R.

Examples of preferred compounds of the general formula (III) are evidentfrom the table below.

    ______________________________________                                        p      q           X            Y                                             ______________________________________                                        0      1           Methylene    Propylene                                     0      0           Propylene    Propylene                                     0      0           Ethylene     Butylene                                      0      0           Ethylene     Pentylene                                     0      0           Ethenylene   Butylene                                      0      1           Methylene    Ethylene                                      0      1           Methylene    Ethenylene                                    0      1           )            Ethenylene                                    0      1           S            Ethenylene                                    0      0           Ethylene     Ethenylene                                    0      0           Ethylene     Ethylene                                      0      2           Benzene nucleus                                            1      1           C--C double bond                                           1      1           Propylene    Zero bridge                                   2      0           Butylene     Zero bridge                                   3      0           Butylene     Zero bridge                                   4      0           Propylene    Zero bridge                                   ______________________________________                                    

In one embodiment of the invention, the secondary amines have thegeneral formula (IV). ##STR2##

In this, X are independently C₁₋₈ --, preferably C₃₋₄ -alkyleneradicals, C₂₋₈ --, preferably C₃₋₄ -alkenylene radicals or form anaromatic ring, in particular an aromatic C₆ ring (benzene ring).

Y is a C₁₋₈ --, preferably C₁₋₄ --, in particular C₁₋₂ -alkyleneradical, C₂₋₈ --, preferably C₂₋₄ --, in particular C₂ -alkenyleneradical, O, S or a C--C single bond.

X and Y may be interrupted as described for formula (III).

In a preferred embodiment, both X radicals form aromatic C₆ nuclei and Yis an oxygen atom, sulfur atom or a methylene radical.

One or more hydrogen atoms bonded to carbon may be replaced bysubstituents as detailed above for the compounds of the formula (III).

Further examples of preferred bicyclic secondary amines areazabicyclo[2.2.1]-heptanes, azabicyclo[2.2.2]octanes,azabicyclo[3.2.1]octanes, azabicyclo[3.3.0]-octanes,azabicyclo[3.2.2]nonanes, azabicyclo[3.3.1]nonanes,azabicyclo[4.2.1]-nonanes, azabicyclo[4.2.2]decanes,azabicyclo[4.3.1]decanes, it being possible for the nitrogen atom to bepresent at any position on the bridges, but not in the bridgeheadposition. The secondary amino group is thus located in the cyclicframework. 1,3,3-Trimethyl-6-azabicyclo[3.2.1]octane and3-azabicyclo[3.2.2]-nonane are preferred.

In one embodiment of the invention, the total number of carbon atoms inthe cyclic, bicyclic or oligocyclic secondary amine is 5 to 40,preferably 6 to 30, in particular 7 to 20 carbon atoms.

The cyclic, bicyclic or oligocyclic secondary amines according to theinvention may have an even greater effectiveness as bleaching efficiencyboosters than the acyclic amines.

In addition, when the secondary amines, in particular the cyclic,bicyclic or oligocyclic secondary amines, are used in enzyme-containingdetergents with bleaching systems, the enzymatic action is not or onlynegligibly adversely affected, or is even improved, by the bleachingsystem. The single wash cycle performance for enzymatically removablestains is thereby significantly improved.

Preparation of the secondary amines used according to the invention isknown. It can take place, for example, by reductive amination ofaldehydes or by amination of nitrites. Cyclic amines can moreover beprepared by reducing the corresponding lactams and bicyclic amines byDiels-Alder reactions.

The preferably cyclic, bicyclic or oligocyclic secondary amine can beemployed as free amine in detergent and cleaner formulations. It canalso be in the form of the ammonium salt, in which case the anion is,for example, a tosylate, sulfate, chloride, bromide or an anion of aninorganic or organic acid.

The anion in this case should be stable to oxidation. Examples ofsuitable inorganic acids for forming the anion are sulfuric acid,phosphoric acid, polyphosphoric acid, boric acid and hydrochloric acid.Other suitable anions are silicates and alumosilicate anions. Examplesof suitable organic acids are carboxylic acids, such as C₁₋₂₅-monocarboxylic acids, C₂₋₂₅ -dicarboxylic acids, C₆₋₂₅ -tricarboxylicacids, butanetetracarboxylic acid, polycarboxylic acids, such aspolyacrylic acid, polymaleic acid, co- and terpolymers of acrylic acidand maleic acid with other monomers, sulfonic acids, such as C₁₋₂₅-alkyl-, aralkyl- and arylsulfonic acids, phosphonic acids, such asC₁₋₂₅ -alkyl-, aralkyl- and aryl-phosphonic acids, and C₁₋₂₅-aminophosphonic acids with 1 to 4 tertiary amino groups and 1 to 6phosphonic acid groups. An example of a salt of secondary amine and apolycarboxylic acid is the salt of the amine with the acrylicacid/maleic acid copolymer Sokalan® CP 45 from BASF AG, it beingpossible to replace the Na⁺ and H⁺ cations normally present in thepolycarboxylate by various amounts of the ammonium ion of the amine.Other examples of suitable anions are fatty acid anions and anions fromcitric acid or methylsulfonate.

The secondary amine is preferably employed in the form of a salt. Inthis case, the salts particularly preferably employed have the anionsnormally present in detergents or bleaches.

BLEACH OR TEXTILE DETERGENT COMPOSITION Bleach

The secondary amines used according to the invention are used asbleaching efficiency boosters or bleach catalysts in bleach or textiledetergent compositions which, in one embodiment of the invention, arebased on active oxygen. These can be inorganic and/or organic peracids(percarboxylic acids) and/or peroxy compounds which, in combination withthe, in particular secondary, amine according to the invention, show astronger bleaching effect than without the combination with the amines,especially for lipophilic and/or lipophobic stains at low temperatures.

Examples are alkali metal perborates or alkali metal carbonateperhydrates, especially the sodium salts.

An example of an organic peracid which can be used is peracetic acidwhich is preferably used in commercial textile laundering or commercialcleaning.

Bleach or textile detergent compositions which can be advantageouslyused contain C₁₋₁₂ -percarboxylic acids, C₈₋₁₆ -dipercarboxylic acids,imidopercaproic acids or aryldipercaproic acids. Preferred examples ofacids which can be used are peracetic acid, linear or branchedmonoperoctanoic, -nonanoic, -decanoic or -dodecanoic acids, diperdecane-and -dodecanedioic acids, mono- and diperphthalic acids, -isophthalicacids and -terephthalic acids, phthalimidopercaproic acid (PAP) andterephthaloyldiamidopercaproic acid (TOCAP). It is likewise possible touse polymeric peracids, for example those containing acrylic acid basicbuilding blocks in which a peroxy functionality is present. Thepercarboxylic acids can be used as free acids or as salts of the acids,preferably alkali metal or alkaline earth metal salts.

The bleach or textile detergent compositions are preferably employed forbleaching textiles, especially stained textiles, particularly preferablywith hydrophobic or lipophilic stains such as chlorophyll from greenplant parts (spinach, grass, leaves) or carotene from vegetables(carrots, tomatoes, paprika). In one embodiment, they are preferablyused for bleaching lipophobic/hydrophilic stains, such as tea.

BLEACH ACTIVATOR

The bleaching efficiency boosting according to the invention due to useof the, in particular secondary, amines according to the invention isparticularly effective on use in activated bleach or textile detergentcompositions. In these cases, the secondary amine is employed incombination with a bleach activator and a peroxy compound which providesactive oxygen. The bleaching effect achieved in this case exceeds thatof an amine-free activated bleach composition, especially for lipophilicstains such as chlorophyll or carotene and/or lipophobic stains such astea. The secondary amines employed according to the invention may beemployed together with other suitable bleach catalysts. Examples thereofare quaternized imines and sulfone imines as described, for example, inU.S. Pat. No. 5,360,568, U.S. Pat. No. 5,360,569 and EP-A-0 453 003, aswell as manganese complexes as described, for example, in WO-A 94/21777.Other metal-containing bleach catalysts which can be used are describedin EP-A-0 458 397, EP-A-0 458 398 and EP-A-0 549 272.

Bleach activators which can be employed in one embodiment of theinvention together with the, in particular secondary, amines accordingto the invention in bleach or textile detergent compositions are, forexample, compounds of the following classes of substances:

Polyacylated sugars or sugar derivatives with C₁₋₁₀ -acyl radicals,preferably acetyl, propionyl, octanoyl, nonanoyl or benzoyl radicals,particularly preferably acetyl radicals, can be used as bleachactivators. Sugars or sugar derivatives which can be used are mono- ordisaccharides and their reduced or oxidized derivatives, preferablyglucose, mannose, fructose, sucrose, xylose or lactose. Particularlysuitable bleach activators of this class of substances are, for example,pentaacetylglucose, xylose tetraacetate,1-benzoyl-2,3,4,6-tetraacetylglucose and1-octanoyl-2,3,4,6-tetraacetylglucose.

Another class of substances which can be used comprisesacyloxybenzenesulfonic acids and their alkali metal and alkaline earthmetal salts, it being possible to use C₁₋₁₄ -acyl radicals. Acetyl,propionyl, octanoyl, nonanoyl and benzoyl radicals are preferred,especially acetyl radicals and nonanoyl radicals. Particularly suitablebleach activators in this class of substances areacetyloxybenzenesulfonic acid, benzoyloxybenzenesulfonic acid andnonanoyloxybenzenesulfonic acid (NOBS) or isononanoyloxybenzenesulfonicacid (isoNOBS). They are preferably employed in the form of their sodiumsalts.

It is furthermore possible to use O-acyloxime esters, such as acetoneO-acetyloxime, acetone O-benzoyloxime, bis(propylimino) carbonate,bis(cyclohexylimino) carbonate. Acylated oximes which can be usedaccording to the invention are described, for example, in EP-A-0 028432. Oxime esters which can be used according to the invention aredescribed, for example in EP-A-0 267 046.

It is likewise possible to use N-acylcaprolactams, such asN-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam andcarbonylbiscaprolactam.

It is furthermore possible to use

N,N-diacylated and N,N,N',N'-tetraacylated amines, such asN,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine (TAED),N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylatedhydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;

N-alkyl-N-sulfonylcarboxamides, such as N-methyl-N-mesylacetamide orN-methyl-N-mesylbenzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, such asmonoacetylated maleic hydrazide;

O,N,N-trisubstituted hydroxylamines, such asO-benzoyl-N,N-succinyl-hydroxylamine, O-acetyl-N,N-succinylhydroxylamineor O,N,N-triacetylhydroxylamine;

N,N'-diacylsulfamides, such as N,N'-dimethyl-N,N'-diacetylsulfamide orN,N'-diethyl-N,N'-dipropionylsulfamide;

triacylcyanurates, such as triacetylcyanurate or tribenzoylcyanurate;

carboxylic anhydrides, such as benzoic anhydride, m-chlorobenzoicanhydride or phthalic anhydride;

1,3-diacyl-4,5-diacyloxyimidazolines, such as1,3-diacetyl-4,5-diacetoxyimidazoline;

tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2,5-diketopiperazines, such as1,4-diacetyl-2,5-diketopiperazine;

acylation products of propylenediurea and 2,2-dimethylpropylenediurea,such as tetraacetylpropylenediurea;

α-acyloxypolyacylmalonamides, such as α-acetoxy-N,N'-diacetylmalonamide;

diacyldioxohexahydro-1,3,5-triazines, such as1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

It is likewise possible to use 2-alkyl- or2-aryl-(4H)-3,1-benzoxazin-4-ones as described, for example, in EP-B1-0332 294 and EP-B 0 502 013. It is possible to use in particular2-phenyl-(4H)-3,1-benzoxazin-4-one and2-methyl-(4H)-3,1-benzoxazin-4-one.

It is furthermore possible to use cationic nitrites, as described, forexample, in EP 303 520 and EP 458 396 A1. Examples of suitable cationicnitrites are the methosulfates or tosylates oftrimethylammonioacetonitrile, N,N-dimethyl-N-octylammonioacetonitrile,2-(trimethylammonio)propionitrile,2-(trimethylammonio)-2-methylpropionitrile. Also suitable are themethosulfates of N-methylpiperazinio-N,N'-diacetonitrile andN-methylmorpholinioacetonitrile (MMA).

The bleach activators which can be used according to the invention arepreferably in the solid state of aggregation at room temperature becauseintimate contact of the amine with the bleach activator before use maybe disadvantageous for achieving the optimal bleaching effect.Crystalline bleach activators which are particularly suitable accordingto the invention are tetraacetylethylenediamine (TAED), NOBS, isoNOBS,carbonylbiscaprolactam (CBC), benzoylcaprolactam, bis(2-propylimino)carbonate, bis(cyclohexylimino) carbonate, acetone O-benzoyloxime and2-phenyl-(4H)-3,1-benzoxazin-4-one, anthranil, phenylanthranil,N-methylmorpholinoacetonitrile, N-octanoylcaprolactam (OCL) andN-methylpiperazine-N,N'-diacetonitrile, and liquid or poorlycrystallizing bleach activators formulated as solid product. An exampleof a suitable formulation of such activators is given in the GermanPatent Application having the file reference 196 09 953.6, which is nota prior publication.

BLEACH STABILIZER

In one embodiment of the present invention, the bleach or textiledetergent compositions which, for example, can be employed in detergentsand cleaners additionally contain one or more bleach stabilizers. Thesecomprise additives able to adsorb, bind or complex traces of heavymetals. Examples of additives which can be used according to theinvention with a bleach-stabilizing action are polyanionic compounds,such as polyphosphates, polycarboxylates, polyhydroxypolycarboxylates,soluble silicates as completely or partially neutralized alkali metal oralkaline earth metal salts, in particular as neutral Na or Mg salts,which are relatively weak bleach stabilizers. Examples of strong bleachstabilizers which can be used according to the invention are complexingagents such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid(NTA), methyl-glycinediacetic acid (MGDA), β-alaninediacetic acid (ADA),ethylenediamine-N,N'-disuccinate (EDDS) and phosphonates such asethylenediaminetetramethylenephosphonate,diethylenetriaminepentamethylenephosphonate orhydroxyethylidene-1,1-diphosphonic acid in the form of the acids or aspartially or completely neutralized alkali metal salts. The complexingagents are preferably employed in the form of their Na salts.

The detergents according to the invention preferably contain at leastone bleach stabilizer, particularly preferably at least one of theabovementioned strong bleach stabilizers.

In one embodiment of the invention, the bleach or textile detergentcompositions described may, in the area of textile laundering, ofbleaching and of cleaning in the household and in the commercial sector,contain virtually all conventional ingredients of detergents, bleachesand cleaners. It is possible in this way to design, for example,compositions which are specifically suitable for textile treatment atlow temperatures, and those which are suitable in several temperatureranges up to the traditional boiling wash range.

The main ingredients of textile detergents, bleaches and cleaners are,besides the bleach composition which consists of bleach and, inparticular, secondary, amine according to the invention, with or withoutbleach activator, builders, that is to say inorganic builders and/ororganic cobuilders, and surfactants, in particular anionic and/ornonionic surfactants. Besides these, it is also possible for otherconventional auxiliaries and additives such as fillers, complexingagents, phosphonates, dyes, corrosion inhibitors, antiredepositionagents and/or soil release polymers, color transfer inhibitors, bleachcatalysts, peroxide stabilizers, electrolytes, optical brighteners,enzymes, perfume oils, foam regulators and activating substances to bepresent in these compositions if this is expedient.

INORGANIC BUILDERS

Suitable inorganic builders are all conventional inorganic builders,such as alumosilicates, silicates, carbonates and phosphates.

Examples of suitable inorganic builders are alumosilicates withion-exchanging properties, such as zeolites. Various types of zeolitesare suitable, expecially zeolites A, X, B, P, MAP and HS in their Naform, or in forms in which Na is partly replaced by other cations, suchas Li, K, Ca, Mg or ammonium. Suitable zeolites are described, forexample, in EP-A 038 591, EP-A 021 491, EP-A 087 035, U.S. Pat. No.4,604,224, GB-A2 013 259, EP-A 522 726, EP-A 384 070 and WO 94/24251.

Other suitable inorganic builders are, for example, amorphous orcrystalline silicates, such as amorphous disilicates, crystallinedisilicates such as the sheet silicate SKS-6 (manufactured by Hoechst).The silicates can be employed in the form of their alkali metal,alkaline earth metal or ammonium salts. Na, Li and Mg silicates arepreferably employed.

ANIONIC SURFACTANTS

Suitable anionic surfactants are, for example, fatty alcohol sulfates offatty alcohols with 8 to 22, preferably 10 to 18, carbon atoms, such asC₉ -C₁₁ -alcohol sulfates, C₁₂ -C₁₃ -alcohol sulfates, cetyl sulfate,myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fattyalcohol sulfate. Other suitable anionic surfactants are sulfatedethoxylated C₈ -C₂₂ -alcohols (alkyl ether sulfates) and their solublesalts. Compounds of this type are prepared, for example, by firstlyalkoxylating a C₈ -C₂₂ --, preferably a C₁₀ -C₁₈ --, alcohol, such as afatty alcohol, and subsequently sulfating the alkoxylation product.Ethylene oxide is preferably used for the alkoxylation, employing 2 to50, preferably 3 to 20 mol of ethylene oxide per mole of fatty alcohol.However, the alkoxylation of the alcohols can also take place withpropylene oxide alone or together with butylene oxide. Also suitable arealkoxylated C₈ -C₂₂ -alcohols which contain ethylene oxide and propyleneoxide or ethylene oxide and butylene oxide. The alkoxylated C₈ -C₂₂-alcohols may contain the ethylene oxide, propylene oxide and butyleneoxide units in the form of blocks or in random distribution.

Other suitable anionic surfactants are alkanesulfonates, such as C₈ -C₂₄--, preferably C₁₀ -C₁₈ --, alkanesulfonates, and soaps, such as thesalts of C₈ -C₂₄ -carboxylic acids.

Other suitable anionic surfactants are linear C₉ -C₂₀-alkylbenzenesulfonates (LAS).

Other suitable anionic surfactants are N-acylsarcosinates with aliphaticsaturated or unsaturated C₈ -C₂₅ -acyl radicals, preferably C₁₀ -C₂₀-acyl radicals, for example N-oleoylsarcosinate.

The anionic surfactants are added to the detergent preferably in theform of salts. Suitable cations in these salts are alkali metal ionssuch as sodium, potassium and lithium, and ammonium ions, such ashydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium ions.

NONIONIC SURFACTANTS

Examples of suitable nonionic surfactants are alkoxylated C₈ -C₂₂-alcohols, such as fatty alcohol alkoxylates or oxoalcohol alkoxylates.The alkoxylation can be carried out with ethylene oxide, propylene oxideand/or butylene oxide. It is possible to employ as surfactant in thiscase all alkoxylated alcohols which contain at least two molecules of anabovementioned alkylene oxide in the adduct. Also suitable in thisconnection are block polymers of ethylene oxide, propylene oxide and/orbutylene oxide, or adducts which contain said alkylene oxides in randomdistribution. From 2 to 50, preferably 3 to 20, mol of at least onealkylene oxide are used per mole of alcohol. Ethylene oxide ispreferably employed as alkylene oxide. The alcohols preferably have 10to 18 carbon atoms.

Another class of suitable nonionic surfactants comprises alkylphenolethoxylates with C₆ -C₁₄ -alkyl chains and 5 to 30 mol of ethylene oxideunits.

Another class of nonionic surfactants comprises alkyl polyglucosideswith 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain.These compounds usually contain from 1 to 20, preferably 1.1 to 5,glucoside units.

Another class of nonionic surfactants comprises N-alkylglucamides of thegeneral structure IV or V: ##STR3## where R⁶ is C₆ -C₂₂ -alkyl, R⁷ is Hor C_(1-C) ₄ -alkyl and R⁸ is a polyhydroxyalkyl radical with 5 to 12carbon atoms and at least 3 hydroxyl groups. R⁶ is preferably C₁₀ -C₁₈-alkyl, R⁷ is preferably methyl and R⁸ is preferably a C₅ or C₆ radical.Compounds of this type are obtained, for example, by acylation ofreductively aminated sugars with the chlorides of C₁₀ -C₁₈ -carboxylicacids.

The detergents according to the invention preferably contain C₁₀ -C₁₆alcohols ethoxylated with 3-12 mol of ethylene oxide, particularlypreferably ethoxylated fatty alcohols as nonionic surfactants.

ORGANIC COBUILDERS

Examples of low molecular weight polycarboxylates suitable as organiccobuilders are:

C₄ -C₂₀ -di-, -tri- and -tetracarboxylic acids, such as succinic acid,propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acidswith C₂ -C₁₆ -alkyl- or -alkenyl radicals;

C₄ -C₂₀ -hydroxy carboxylic acids, such as malic acid, tartaric acid,gluconic acid, glucaric acid, citric acid, lactobionic acid andsucrosemono-, -di- and -tricarboxylic acids;

aminopolycarboxylates, such as nitrilotriacetic acid,methylglycinediacetic acid, alaninediacetic acid,ethylenediaminetetraacetic acid and serinediacetic acid;

salts of phosphonic acids, such as hydroxyethanediphosphonic acid,ethylenediaminetetra(methylenephosphonate) anddiethylenetriaminepenta(methylenephosphonate).

Examples of oligomeric or polymeric polycarboxylates suitable as organicco-builders are:

oligomaleic acids as described, for example, in EP-A-451 508 andEP-A-396 303;

co- and terpolymers of unsaturated C₄ -C₈ -dicarboxylic acids, possibleco-monomers which may be present being monoethylenically unsaturatedmonomers

from group (i) in amounts of up to 95% by weight

from group (ii) in amounts of up to 60% by weight

from group (iii) in amounts of up to 20% by weight.

Examples of unsaturated C₄ -C₈ -dicarboxylic acids suitable in this caseare maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleicacid is preferred.

The group (i) comprises monoethylenically unsaturated C₃ -C₈-monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonicacid and vinylacetic acid. Preferably employed from group (i) areacrylic acid and methacrylic acid.

Group (ii) comprises monoethylenically unsaturated C₂ -C₂₂ -olefins,vinyl alkyl ethers with C₁ -C₈ -alkyl groups, styrene, vinyl esters ofC₁ -C₈ -carboxylic acids, (meth)acrylamide and vinylpyrrolidone.Preferably employed from group (ii) are C₂ -C₆ -olefins, vinyl alkylethers with C_(1-C) ₄ -alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) comprises (meth)acrylic esters of C₁ -C₈ -alcohols,(meth)acrylnitrile, (meth)acrylamides of C₁ -C₈ -amines,N-vinylformamide and vinylimidazole.

If the polymers contain vinyl esters as monomers of group (ii) these canalso be partially or completely hydrolyzed to vinyl alcohol structuralunits. Suitable co- and terpolymers are disclosed, for example, in U.S.Pat. No. 3,887,806 and DE-A 43 13 909.

Copolymers of dicarboxylic acids which are suitable and preferred asorganic cobuilders are the following:

copolymers of maleic acid and acrylic acid in the ratio of 10:90 to 95:5by weight,

particularly preferably those in the ratio of from 30:70 to 90:10 byweight, with molecular weights of from 10,000 to 150,000;

terpolymers of maleic acid, acrylic acid and a vinyl ester of a C₁ -C₃-carboxylic acid in the ratio of from 10 (maleic acid):90 (acrylicacid+vinyl ester) to 95 (maleic acid):5 (acrylic acid+vinyl ester) byweight, it being possible for the ratio of acrylic acid to vinyl esterto vary in the range from 20:80 to 80:20 by weight, and particularlypreferably

terpolymers of maleic acid, acrylic acid and vinyl acetate or vinylpropionate in the ratio of from 20 (maleic acid):80 (acrylic acid+vinylester) to 90 (maleic acid):10 (acrylic acid+vinyl ester) by weight, itbeing possible for the ratio of acrylic acid to the vinyl ester to varyin the range from 30:70 to 70:30 by weight;

copolymers of maleic acid with C₂ -C₈ -olefins in the molar ratio from40:60 to 80:20, with copolymers of maleic acid with ethylene, propyleneor isobutene in the molar ratio 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weightcarbohydrates or hydrogenated carbohydrates, see U.S. Pat. No.5,227,446, DE-A-44 15 623, DE-A-43 13 909, are likewise suitable asorganic cobuilders.

Suitable unsaturated carboxylic acids in this connection are, forexample, maleic acid, fumaric acid, itaconic acid, citraconic acid,acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, andmixtures of acrylic acid and maleic acid, which are grafted on inamounts of from 40 to 95% of the weight of the component to be grafted.

It is additionally possible for up to 30% by weight, based on thecomponent to be grafted, of other monoethylenically unsaturated monomersto be present for modification. Suitable modifying monomers are theabovementioned monomers of groups (ii) and (iii).

Suitable as grafting base are degraded polysaccharides, such asacidically or enzymatically degraded starches, inulins or cellulose,reduced (hydrogenated or reductively aminated) degraded polysaccharides,such as mannitol, sorbitol, aminosorbitol and glucamine, andpolyalkylene glycols with molecular weights of up to M_(w) =5,000 suchas polyethylene glycols, ethylene oxide/propylene oxide or ethyleneoxide/butylene oxide block copolymers, random ethylene oxide/propyleneoxide or ethylene oxide/butylene oxide copolymers, alkoxylated mono- orpolyhydric C₁ -C₂₂ -alcohols, see U.S. Pat. No. 4,746,456.

Preferably employed from this group are grafted degraded or degradedreduced starches and grafted polyethylene oxides, employing from 20 to80% by weight of monomers, based on the grafting component, in the graftpolymerization. A mixture of maleic acid and acrylic acid in the ratioof from 90:10 to 10:90 by weight is preferably employed for thegrafting.

Polyglyoxylic acids suitable as organic cobuilders are described, forexample, in EP-B-001 004, U.S. Pat. No. 5,399,286, DE-A-41 06 355 andEP-A-656 914. The end groups of the polyglyoxylic acids may have variousstructures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acidssuitable as organic cobuilders are disclosed, for example, in EP-A-454126, EP-B-511 037, WO 94/01486 and EP-A-581 452.

Also preferably used as organic cobuilders are polyaspartic acid orcocondensates of aspartic acid with other amino acids, C₄ -C₂₅ -mono- or-dicarboxylic acids and/or C₄ -C₂₅ -mono- or -diamines. Polyasparticacids prepared in phosphorus-containing acids and modified with C₆ -C₂₂-mono- or -dicarboxylic acids or with C₆ -C₂₂ -mono- or -diamines areparticularly preferably employed.

Condensation products of citric acid with hydroxy carboxylic acids orpolyhydroxy compounds which are suitable as organic cobuilders aredisclosed, for example, in WO 93/22362 and WO 92/16493.Carboxyl-containing condensates of this type normally have molecularweights of up to 10,000, preferably up to 5,000.

ANTIREDEPOSITION AGENTS AND SOIL RELEASE POLYMERS

Suitable soil release polymers and/or antiredeposition agents fordetergents are, for example:

polyesters of polyethylene oxides with ethylene glycol and/or propyleneglycol and aromatic dicarboxylic acids or aromatic and aliphaticdicarboxylic acids;

polyesters of polyethylene oxides, which are endgroup-capped at one end,with di- and/or polyhydric alcohols and dicarboxylic acid.

Polyesters of this type are disclosed, for example, in U.S. Pat. No.3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985,EP-A-272 033 and U.S. Pat. No. 5,142,020.

Other suitable soil release polymers are amphiphilic graft or othercopolymers of vinyl and/or acrylic esters on polyalkylene oxides (seeU.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-37 11 299, U.S.Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126)or modified celluloses, such as methylcellulose, hydroxypropylcelluloseor carboxymethylcellulose.

COLOR TRANSFER INHIBITORS

Color transfer inhibitors which are employed are, for example, homo- andcopolymers of vinylpyrrolidone, of vinylimidazole, of vinyloxazolidoneand of 4-vinylpyridine N-oxide with molecular weights of from 15,000 to100,000, and crosslinked fine-particle polymers based on these monomers.The use of such polymers mentioned herein is disclosed in DE-B-22 32353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.

ENZYMES

In one embodiment of the invention, the bleach compositions containingat least one secondary amine are used in enzyme-containing detergentsand cleaners. In many of these cases, the enzymes show an effect whichenhances the action of the bleach composition and which is particularlymarked on use of the bleach compositions according to the invention.Suitable enzymes in this connection are, for example, proteases,amylases, lipases and cellulases, especially proteases. It is possibleto use several enzymes in combination.

On the other hand, the bleach compositions according to the inventioncontaining at least one secondary amine adversely affect the action ofthe enzymes, in particular the single wash cycle performance, extremelyslightly or not at all. Known bleach compositions by contrast often showan enzyme-damaging effect, which diminishes the effectiveness oractivity of the enzymes. It is possible with the bleach compositionsaccording to the invention to avoid this enzyme damage and achieve ahigh enzyme activity. This is particularly the case on use of cyclic,bicyclic or oligocyclic secondary amines.

Besides use in detergents and cleaners for household textile laundering,the bleach compositions which can be used according to the invention canalso be employed in commercial textile laundering and commercialcleaning. For use in this sector, as a rule, peracetic acid is employedas bleach and is added as aqueous solution to the wash liquor. In thisarea of application, the secondary amine used according to the inventioncan either be added separately as single component in the washing orcleaning process, or be previously mixed together with other ingredientsand then added as mixture.

USE IN TEXTILE DETERGENTS

Preferably the claimed amines are used in textile detergentscompositions comprising at least one bleach and at least one bleachactivator, which is preferably solid at room temperature, with orwithout a bleach stabilizer and with or without other bleach catalysts.

In one embodiment, the textile detergents comprising at least one, inparticular secondary, amine according to the invention and based onperoxy compounds and is percarboxylic acids comprise from 0.5 to 40% byweight, preferably 2.5 to 30% by weight, particularly preferably 5 to25% by weight, of peroxy compounds or peracids, from 0 to 20% by weight,preferably from 0.1 to 20% by weight, preferably 0.5 to 10% by weight,particularly preferably 0.5 to 6.0% by weight, of bleach activators andfrom 0.01 to 5% by weight, preferably 0.05 to 2% by weight, particularlypreferably 0.1 to 1% by weight, of at least one, in particularsecondary, amine according to the invention.

In this case it is sufficient to incorporate catalytically activeamounts of the secondary amine, as indicated above, in the bleachcompositions. Even when such small amounts of secondary amines are usedthere is felt to be a strong enhancement of bleaching. On use of thesecondary amines it is possible to improve considerably the efficiencyof bleach compositions, especially cold bleach compositions and, inparticular, with hydrophobic stains. The weaknesses of commercial bleachactivators can thus be specifically compensated by using secondaryamines, so that highly efficient bleaching is possible at lowtemperatures.

The amines to be used according to the invention are preferably employedin powder or granular detergents. These can be classic heavy dutydetergents or concentrated or compact detergents.

A typical powder or granular heavy duty detergent according to theinvention can have, for example, the following composition:

0.5-50% by weight, preferably 5-30% by weight, of at least one anionicand/or nonionic surfactant,

0.5-60% by weight, preferably 15-40% by weight, of at least oneinorganic builder,

0-20% by weight, preferably 0.5-8% by weight, of at least one organicco-builder,

2-35% by weight, preferably 5-30% by weight, of an inorganic bleach,

0.1-20% by weight, preferably 0.5-10% by weight, of a bleach activator,possibly mixed with other bleach activators,

0.005-2.5% by weight, preferably 0.1-1.0% by weight, of a described, inparticular secondary, amine according to the invention,

0-1% by weight, preferably up to a maximum of 0.5% by weight, of ableach catalyst,

0-5% by weight, preferably 0-2.5% by weight, of a polymeric colortransfer inhibitor,

0-1.5% by weight, preferably 0.1-1.0% by weight, of protease,

0-1.5% by weight, preferably 0.1-1,0% by weight, of lipase,

0-1.5% by weight, preferably 0.2-1.0% by weight, of a soil releasepolymer,

ad 100% conventional auxiliaries and additives and water.

Inorganic builders preferably employed in detergents are sodiumcarbonate, sodium bicarbonate, zeolites A and P, and amorphous andcrystalline Na silicates.

Organic cobuilders preferably employed in detergents are acrylicacid/maleic acid copolymers, acrylic acid/maleic acid/vinyl esterterpolymers and citric acid.

Inorganic bleaches preferably employed in detergents are sodiumperborate and sodium carbonate perhydrate.

Inorganic surfactants preferably employed in detergents are fattyalcohol sulfates, linear alkylbenzenesulfonates (LAS) and soaps, withthe LAS content preferably being below 8% by weight, particularlypreferably below 4% by weight.

Nonionic surfactants preferably employed in detergents are C₁₁ -C₁₇ -oxoalcohol ethoxylates with 3-13 ethylene oxide units, C₁₀ -C₁₆ -fattyalcohol ethoxylates with 3-13 ethylene oxide units, and ethoxylatedfatty or oxo alcohols additionally alkoxylated with 1-4 propylene oxideor butylene oxide units.

Preferably the claimed amines are used in textile detergentscompositions comprising at least one enzyme.

Enzymes preferably employed in detergents are protease, lipase andcellulase, the most preferred enzyme is protease. As a rule, thecommercial enzymes are added to the detergent in amounts of from 0.05 to2.0% by weight, preferably 0.2 to 1.5% by weight, of the formulatedenzyme. Examples of suitable proteases are Savinase, Desazym andEsperase (manufactured by Novo Nordisk). An example of a suitable lipaseis Lipolase (manufactured by Novo Nordisk). An example of a suitablecellulase is Celluzym (manufactured by Novo Nordisk).

Antiredeposition agents and soil release polymers preferably employed indetergents are graft polymers of vinyl acetate on polyethylene oxide ofmolecular weight 2,500-8,000 in the ratio of from 1.2:1 to 3.0:1 byweight, polyethylene terephthalates/oxyethylene terephthalates ofmolecular weight 3,000 to 25,000 from polyethylene oxides of molecularweight 750 to 5,000 with terephthalic acid and ethylene oxide and amolar ratio of polyethylene terephthalate to polyoxyethyleneterephthalate of from 8:1 to 1:1, and block polycondensates as disclosedin DE-A-44 03 866.

Color transfer inhibitors preferably employed in detergents are solublevinylpyrrolidone and vinylimidazole copolymers with molecular weightsabove 25,000, and fine-particle crosslinked polymers based onvinylimidazole.

The powder or granular detergents according to the invention may containup to 60% by weight of inorganic fillers. Sodium sulfate is normallyused for this purpose. However, the detergents according to theinvention preferably have a low filler content of only up to 20% byweight, particularly only up to 8% by weight.

The detergents according to the invention may have apparent densitiesvarying in the range from 300 to 1,200, in particular 500 to 950, g/l.Modern compact detergents have, as a rule, high apparent densities and agranular structure.

Besides combined detergents and bleaches, suitable formulations of thedescribed bleach compositions for textile laundering are alsocompositions which are used as additives to peroxide-containing orperoxide-free detergents. They essentially contain the bleachcomposition consisting of bleach and secondary amine, with or withoutbleach activator, and, where appropriate, other auxiliaries andadditives, especially stabilizers, pH regulators, thickeners andsurfactants.

The present invention also relates to bleach additives in bleach ortextile detergent compositions for textile laundering of the followingcomposition:

5-50% by weight, preferably 15-35% by weight, of inorganic peroxycompound,

1-30% by weight, preferably 5-25% by weight, of bleach activators,

0.01-5.0, preferably 0.1-2.5, % by weight of a described amine,

0-5% by weight, preferably 0.1-3% by weight, of peroxide stabilizers,

0-40% by weight, preferably 5-30% by weight, of pH regulators,

ad 100% by weight of other conventional auxiliaries and additives.

Examples of compositions of heavy duty detergents which can be used inthe household are compiled in the following table.

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activators,and

(c) 0.1-1.0% by weight, preferably 0.25-0.60% by weight, in particular0.25-0.45% by weight, of secondary amines according to formula (I),(III) or (IV) preferably according to formula (I), where n has the value0, the radical R¹ is a C₆₋₁₄ hydrocarbyl radical or -hydroxyhydrocarbylradical which preferably has zero to one branch, and the radical R² is aC₁₋₅ -hydrocarbyl radical, preferably a methyl radical.

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0.1-20% by weight of at least one bleach activator from the group oftetraacetylethylenediamine (TAED), NOBS, isoNOBS,carbonylbis-caprolactam, benzoylcaprolactam, bis(2-propylimino)carbonate, bis(cyclohexylimino) carbonate, acetone O-benzoyloxime,anthranil (2-methyl-(4H)-3,1-benzoxazin-4-one), phenylanthranil,N-methylmorpholinoacetonitrile, (2-phenyl-(4H)-3,1-benzoxazin-4-one),N-methylpiperazine-N,N'-diacetonitrile and N-octanoylcaprolactam (OCL)and

(c) more than 0.1 to less than 1.0% by weight, preferably 0.15-0.95% byweight, of secondary amines according to formula (I), wherein preferablyn has the value 0, the radical R¹ is a C₆₋₁₄ -hydrocarbyl radical or-hydroxycarbyl radical which preferably has zero to one branch, and theradical R² is a C₁₋₅ -hydrocarbyl radical, preferably a methyl radicalor according to formula (III) or (IV)

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activatorsand

(c) 0.01-5% by weight of secondary amines of the general formula R¹ R²NH or of the corresponding ammonium salts, where the radical R¹ is analkyl radical or a phenylalkyl radical with 7 to 12 carbon atoms, andthe radical R² is C₁ -C₄ -alkyl, preferably 0.05-3% by weight ofsecondary amines from the group of N-heptyl-N-methylamine,N-octyl-N-methylamine, N-nonyl-N-methylamine, N-decyl-N-methylamine,N-2-propylheptyl-N-methylamine, N-2-ethylhexyl-N-methylamine,N-dodecyl-N-methylamine, N-2-ethylhexyl-N-butylamine andN-2-phenylethyl-N-methylamine.

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of at least one bleach from the group of sodiumperborates, sodium carbonate perhydrates, C₁ -C₁₂ -percarboxylic acids,C₈ -C₁₆ -dipercarboxylic acids, imidopercaproic acids andaryldipercaproic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activatorsand

(c) more than 0.1 to less than 1.0% by weight, preferably 0.15-0.95% byweight, of secondary amines according to formula (I), wherein preferablyn has the value 0, the radical R¹ is a C₆₋₁₄ -hydrocarbyl radical or-hydroxycarbyl radical which preferably has zero to one branch, and theradical R² is a C₁₋₅ -hydrocarbyl radical, preferably a methyl radicalor according to formula (III) or (IV)

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activators,and

(c) 0.1 to less than 0.5% by weight, preferably 0.25-0.45% by weight, ofsecondary amines according to the invention.

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0.1-20% by weight of at least one bleach activator from the group oftetraacetylethylenediamine (TAED), NOBS, isoNOBS,carbonylbis-caprolactam, benzoylcaprolactam, bis(2-propylimino)carbonate, bis(cyclohexylimino) carbonate, acetone O-benzoyloxime,anthranil (2-methyl-(4H)-3,1-benzoxazin-4-one, phenylanthranil(2-phenyl-(4H)-3,1-benzoxazin-4-one), N-methylmorpholinoacetonitrile,N-methylpiperazine-N,N'-diacetonitrile and N-octanoylcaprolactam (OCL)and

(c) more than 0.1 to less than 0.5% by weight, preferably 0.15-0.45% byweight, of secondary amines according to the invention.

In one embodiment of the invention, the bleach or textile detergentcomposition comprises

(a) 0.5-40% by weight of at least one bleach from the group of sodiumperborates, sodium carbonate perhydrates, C₁ -C₁₂ -percarboxylic acids,C₈ -C₁₆ -dipercarboxylic acids, imidopercaproic acids andaryldipercaproic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activatorsand

(c) more than 0.1 to less than 0.5% by weight, preferably 0.15-0.45% byweight, of secondary amines according to the invention.

The invention additionally relates to a bleach or textile detergentcomposition comprising

(a) 0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids,

(b) 0-20% by weight, preferably 0.1-20% by weight, of bleach activators

(c) 0.01-5, preferably 0.1-1, % by weight of secondary amines accordingto the formulae (III) or (IV).

In one embodiment of the invention, the textile detergent composition isessentially phosphate-free.

In one embodiment of the invention, the textile detergent according tothe invention is essentially free of linear alkylbenzenesulfonates andis preferably based on fatty alcohol sulfonates.

In one embodiment of the invention, the textile detergent compositionaccording to the invention comprises at least one polycarboxylate,preferably in an amount of from 0.1 to 7.5% by weight.

The invention also relates to the use of a bleach or textile detergentcomposition for removing hydrophobic and/or hydrophilic stains ontextiles.

                                      TABLE 1                                     __________________________________________________________________________    Compositions of heavy duty detergents                                                          I   II  III IV  V   VI  VII                                  __________________________________________________________________________    PVP (K value 30) 1.5                                                          VI/VP copolymer (K value 30)                                                                       1.0             0.6                                      VI/VP copolymer crosslinked      1.0     1.0                                  AA/MA (M = 70,000)       5.0                                                  AA/MA (M= 10,000)                        5.0                                  AA/MA/VAc terpoymer (M = 20,000)     5.0                                      Oligomaleicc acid                5.0                                          Polyaspartic acid                                                                              7.5                                                          Na perborate monohydrate                                                                       15  15          15      7.5                                  Na percarbonate          18  15      18                                       TEAD                         5.0     4.2 2.0                                  Carbonylbiscaprolactam                                                                         4.0     5.0     2.9                                          N-Octyl-N-methylamine                                                                          0.25                                                                              0.3 0.5 0.5 0.3 0.6 0.15                                 Na lauryl sulfate    6.0 12.0                                                                              6.0 5.5                                          Linear alkylbenzenesulfonate Na salt                                                           3.1 1.7 0.8         6.5                                      Soap             2.8 0.6 0.4 2.5 1.5     2.4                                  C.sub.13 /C.sub.15 oxo alcohol * 3 EO                                                              3.0                                                      C.sub.13 /C.sub.15 oxo alcohol * 7 EO                                                          4.7     4.7 13.5                                                                              4.0 6.5                                      C.sub.13 /C.sub.15 oxo alcohol * 10 EO                                                             3.0                                                      C.sub.12 /C.sub.14 -fatty alcohol * 7 EO 10.0                                 Lauryl alcohol * 13 EO               5,0                                      Zeolite A        25  25  15      30  15  35                                   Zeolite P                    40                                               SKS-6                    14          15                                       Na disilicate    2.5 3.9     0.5 4.5     1.5                                  Mg silicate      1.0     0.8     1.0 1.0 0.6                                  Sodium sulfate   20  2.5 3.2 2.0 1.5 5.5 3.4                                  Sodium bicarbonate       9.0 6.5                                              Sodium carbonate 12.0                                                                              13.6        10.0                                                                              8.0 9.8                                  Soil release polymer 1                                                                             0.4         0.5                                          Soil release polymer 2                                                                         1.0             0.5 0.8 1.0                                  Carboxymethylcellulose                                                                         0.6 1.3 0.6 1.0 0.6 0.6 0.5                                  Dequest 2046 ®           0.5                                              Citric acid          6.8 5.0         2.5 3.8                                  Lipase                           1.0                                          Protease             1.0         1.0 0.5 0.6                                  Cellulase                                0.6                                  Water            to 100                                                                            to 100                                                                            to 100                                                                            to 100                                                                            to 100                                                                            to 100                                                                            to 100                               __________________________________________________________________________     Soil release polymer 1 = Graft polymer of vinyl acetate on polyethylene       glycol of molecular weight 6,000, molecular weight of the graft polymer       24,000                                                                        Soil release polymer 2 = Polyethylene terephthalate/polyoxyethylene           terephthalate of molecular weight 8,000                                       Dequest 2046 ® = EthylenediamineN,N,N',Ntetra(methylenephosphonate)       SKS6 = Commercial sheet silicate, manufactured by: Hoechst AG            

The invention is illustrated in detail by means of examples below.

Detergent compositions III and IV described above were used in theexamples according to the invention. The washing processes were carriedout in this case in a Launder-O-meter, Atlas standard type, under thefollowing conditions:

                  TABLE 2                                                         ______________________________________                                        Washing conditions                                                            ______________________________________                                        Machine    Launder-O-meter                                                    Cycles     1                                                                  Time       30 min                                                             Temperatures                                                                             22° C., 38° C. and 60° C.                     Water hardness                                                                           3.0 mmol/l                                                         Test fabric                                                                              2.5 g test fabric with chlorophyll stain (WFK: CFT                            AS-4)                                                                         plus 4 × 2.5 g cotton ballast fabric                         Amount of liquor                                                                         250 ml                                                             Liquor ratio                                                                             1:20                                                               Detergent  Nos. III and IV from Tab. 1 using the activator                               indicated in Tab. 3 and the percarboxylic                                     acid indicated in Tab. 4, and using the amines                                indicated in Tabs. 3 and 4 in place of N-methyl-N-                            octylamine                                                         Detergent  4.5 g/l                                                            concentration                                                                 ______________________________________                                    

The bleaching effect of the detergent composition was determined bymeasuring the color strength of the test fabric. This measurement tookplace by photometry. The color strengths of each of the test stainsbefore and after washing were determined from the reflectancemeasurements on the individual test fabrics at 18 wavelengths in therange from 400 to 700 nm at 20 nm intervals by the method described inA. Kud, Seifen, Ole, Fette, Wachse 119, (1993) 590-594, and the absolutebleaching effect A_(abs) was calculated therefrom in %. The absolutebleaching effect A_(abs) is defined as follows: ##EQU1##

The amount of secondary amine used in the following examples was 0.5% byweight. Comparative tests were also carried out without use of asecondary amine and without use of a bleach activator and a secondaryamine, and with use of amines not according to the invention (tests withnonylamine and N-octyl-N,N-dimethylamine).

The results of the tests for a number of secondary amines are compiledin Table 3 below:

                                      TABLE 3                                     __________________________________________________________________________    Results of washing tests with soiled test fabric                              Numbers are the absolute bleaching effect A.sub.abs in %                                          Detergent                                                                Bleach                                                                             formu Chlorophyll                                         Sec. amine     activator                                                                          lation                                                                              22° C.                                                                     38° C.                                                                      60° C.                              __________________________________________________________________________    N-Phenylethyl-N-methylamine                                                   N-Methyl-N-nonylamine                                                                        TAED IV    36.1                                                                              42.9 49.5                                       *none          TAED IV    37.5                                                                              45.3 52.6                                       *none          TAED IV    27.0                                                                              34.0 43.4                                                      none IV    23.8                                                                              29.0 39.1                                       N-Heptyl-N-methylamine                                                                       TAED IV    29.4                                                                              43.1 48.0                                       *Nonylamine    TAED IV    21.9                                                                              30.6 40.9                                       *N-Octyl-N,N-dimethylamine                                                                   TAED IV    21.9                                                                              34.2 44.0                                       *none          TAED IV    25.1                                                                              33.8 41.8                                       *none          none IV    23.8                                                                              32.5 38.9                                       N-Hexyl-N-methylamine                                                                        TAED IV    30.9                                                                              44.4 50.7                                       N-Octyl-N-methylamine                                                                        TAED IV    32.2                                                                              45.0 51.7                                       N-Dodecyl-N-methylamine                                                                      TAED IV    32.6                                                                              42.4 49.0                                       N-Ethylhexyl-N-butylamine                                                                    TAED IV    34.0                                                                              42.7 51.8                                       *none          TAED IV    28.7                                                                              35.1 43.7                                       *none          none IV    26.7                                                                              32.4 42.5                                       N-Octyl-N-methylamine                                                                        OCL  III   35.3                                                                              38.5 42.0                                       *none          OCL  III   29.2                                                                              35.8 40.5                                       *none          none III   14.7                                                                              15.2 21.9                                       N-Methyl-N-nonylamine                                                                        MMA  III   32.5                                                                              34.2 41.9                                       N-Methyl-N-nonylamine                                                                        TAED III   31.6                                                                              37.0 49.2                                       *none          MMA  III   28.6                                                                              32.6 38.9                                       *none          TAED III   25.1                                                                              31.8 38.1                                       *none          none III   22.9                                                                              27.3 35.6                                       __________________________________________________________________________     *comparative tests                                                       

The results in Table 3 show that the bleaching effect of the bleachcompositions used according to the invention, using secondary amineswith percarbonate as oxygen-donating bleach and various bleachactivators, on chlorophyll stains provides very good bleaching resultswhich are distinctly superior to the bleaching effect of bleaches aloneor a combination of bleach activator and bleach or a combination ofbleach catalyst, bleach and amines not according to the invention.

In the tests below, percarboxylic acids were additionally employed asbleach, and no bleach activator was added. The results are compiled inTable 4.

                  TABLE 4                                                         ______________________________________                                        Results of washing tests with soiled test fabric                              Numbers are the absolute bleaching effect A.sub.abs in %                               Percar-                                                                       boxylic                                                                             Detergent Chlorophyll                                          Sec. amine acid    formulation                                                                             22° C.                                                                       38° C.                                                                       60° C.                        ______________________________________                                        N-Methyl-N-                                                                   nonylamine                                                                    *none      PAP     IV        45.4  49.3  55.6                                 *none      PAP     IV        34.3  41.3  46.5                                            none    IV        27.9  31.6  44.3                                 N-Phenylethyl-N-                                                              methylamine                                                                   N-Methyl-N-                                                                              TOCAP   IV        33.9  39.2  47.5                                 nonylamine                                                                    *none      TOCAP   IV        35.0  42.1  48.8                                 *none      TOCAP   IV        28.6  35.4  43.5                                            none    IV        23.8  29.0  39.1                                 ______________________________________                                         *comparative tests                                                       

The results in Table 4 show that the bleaching effect on use of thesecondary amine according to the invention in the bleach compositionsprovides considerably better bleaching results for chlorophyll stainsthan without use of the secondary amines or of the percarboxylic acid.

Washing tests were carried out with lipophilic or lipophobiccontaminations of soiled test fabrics for a number of cyclic andbicyclic secondary amines. The stains used for this purpose werechlorophyll, tea and carotene. Formulation III was used as detergentformulation. The results are compiled in Tables 5 and 6 below.

                  TABLE 5                                                         ______________________________________                                        Results of washing tests at 38° C. with soiled test fabric;            numbers are                                                                   absolute bleaching effect A.sub.abs in %                                              Bleach    Detergent Chloro-                                           Sec. amine                                                                            activator formulation                                                                             phyll Tea   Carotene                              ______________________________________                                        Azacyclo-                                                                             TAED      III       31.6  76.3  84.1                                  nonane                                                                        Azacyclo-                                                                             TAED      III       32.7  76.8  83.3                                  heptane                                                                       3-Azabi-                                                                              TAED      III       29.7  70.5  80.0                                  cyclo-3.3.2-                                                                  nonane                                                                        *none             III       14.7  36.5  71.2                                  *none   TAED      III       18.4  69.2  71.8                                  ______________________________________                                         *Comparative tests                                                       

                  TABLE 6                                                         ______________________________________                                        Results of washing tests at 30° C. with soiled test fabric;            numbers are                                                                   absolute bleaching effect A.sub.abs in %                                              Bleach    Detergent Chloro-                                           Sec. amine                                                                            activator formulation                                                                             phyll Tea   Carotene                              ______________________________________                                        Azacyclo-                                                                             TAED      III       32.1  69.6  64.9                                  heptane                                                                       *none   none      III       12.5  38.1  56.4                                  *none   TAED      III       15.0  64.1  55.4                                  ______________________________________                                         *Comparative tests                                                       

The results in Tables 5 and 6 show that cyclic and bicyclic secondaryamines show a great improvement in the bleaching effect on combinationwith bleach activators. This effect occurs both with hydrophobic stainssuch as chlorophyll and carotene and with hydrophilic stains such astea.

In another series of tests, the cooperation of activated bleachingsystem consisting of bleach activator and secondary amine with enzymeswas investigated. Protease was used as enzyme. The results of washingtests are compiled in Table 7 below.

                  TABLE 7                                                         ______________________________________                                        Results of washing tests on the action of protease in detergent with          activated bleaching system at 20° C. with soiled test fabric WFK       AS10                                                                          (blood/milk/ink); numbers are absolute bleaching effect A.sub.abs in %                Amount of             Amount of                                       Activator                                                                             activator Sec. amine  sec. amine                                                                            A.sub.abs [%]                           ______________________________________                                        TAED    3.8%      Azacycloheptane                                                                           0.5%    90.4                                    TAED    3.8%      *--                 88.8                                    CBC     3.8%      Azacycloheptane                                                                           0.5%    91.3                                    CBC     3.8%      *--                 87.2%                                   ______________________________________                                         Comparative examples are indicated by * in the tables above.             

The results in Table 7 show that the single wash cycle performance ofthe protease on the enzyme test fabric in the heavy duty detergentformulation with activated bleaching system is higher in the presence ofsecondary amines according to the invention than with formulationscontaining no secondary amine. The bleaching system thus has no adverseeffect on the action of the enzyme in the detergent formulation but, onthe contrary, intensifies its action.

The examples show that the use according to the invention of secondaryamines as bleaching efficiency boosters leads to bleach compositions ordetergent and cleaner compositions which show a considerably improvedbleaching effect. The bleach compositions according to the invention canmoreover be employed in a wide variety of areas of technicalapplication, especially those in which a bleaching effect is to beachieved at a low temperature, preferably not exceeding 40° C.Successful bleaching can be achieved in particular with stains which aredifficult to bleach, such as lipophilic compounds, for examplechlorophyll spots (chlorophyll) or carotene-containing spots, and alsofor lipophobic stains, such as tea. Advantageous effects are achieved inparticular in detergent formulations which comprise enzymes. Use of thesecondary amines according to the invention as bleaching efficiencyboosters makes it possible to increase distinctly the effectiveness ofmany bleach compositions.

We claim:
 1. A method of enhancing the bleaching efficiency of bleachand textile detergent compositions, comprising admixing with bleach andtextile detergent compositions compounds represented by formula (III):##STR4## wherein: p and q independently have an integral value from 0 to4,X is a C₁₋₈ -alkylene radical which can be interrupted by O, S,--O--C(O)--, N--R or --NR--C(O)--, C(O)--, where R is a C₁₋₈ -alkylradical, or X is a C₂₋₈ alkenylene radical, Y is a C₁₋₈ -alkyleneradical which can be interrupted by O, S, --O--C(O)--, N--R or --NR--C(O)--, or Y is a C₂₋₈, alkenylene radical, O, S, --O--C(O)--,--NR--C(O)--, N--R or where R is a C₁₋₈, preferably C₁₋₄ -alkyl radical,or Y is a C--C single bond, or X and Y together form a C--C double bondas long as p+q has a value of at least 2, or a carbon atom of each of Xand Y are linked by a C--C single bond or a C₁₋₈ -alkylene radical orC₂₋₈ -alkenylene radical as long as X and Y are C₁₋₈ -alkylene radicals,or X and Y together form an aromatic ring, as long as p+q has a value ofat least 2, it being possible for one or more hydrogen atoms bonded tocarbon atoms to be replaced by C₁₋₁₀ -hydrocarbyl radicals, C₁₋₁₀-alkoxy radicals, C₆₋₁₂ -aryl radicals or C₆₋₁₂ -aralkyl radicals, orcompounds of the general formula (IV): ##STR5## wherein: each X is,independently, a C₁₋₈ -alkylene radicals, C₂₋₈ -alkenylene radicals oraromatic rings, and Y is a C₁₋₈ alkylene radical, C₂₋₄ -alkenyleneradical, O, S or a C--C single bond, or salts thereof.
 2. The method asclaimed in claim 1, wherein in formula (I) n has the value 0, theradical R¹ is a C₆₋₁₄ -hydrocarbyl radical or -hydroxyhydrocarbylradical, and the radical R² is a C₁₋₅ -hydrocarbyl radical.
 3. Themethod as claimed in claim 1, where the textile detergent compositioncomprises at least one bleach and at least one bleach activator, with orwithout a bleach stabilizer and with or without other bleach catalysts.4. The method as claimed in claim 1, where the textile detergentcomposition comprises at least one enzyme.
 5. The method as claimed inclaim 1, for bleaching hydrophobic stains on textiles.
 6. The method asclaimed in claim 1, wherein the bleaching or washing temperature doesnot exceed 40° C.
 7. A bleach or textile detergent composition,comprising:(a) 0.5-40% by weight of bleach in the form of peroxycompounds and/or percarboxylic acids, (b) 0-20% by weight of bleachactivators, and (c) 0.1-1.0% by weight of secondary amines as defined inclaim
 2. 8. A bleach or textile detergent composition, comprising:(a)0.5-40% by weight of bleach in the form of peroxy compounds and/orpercarboxylic acids, (b) 0.1-20% by weight of at least one bleachactivator selected from the group consisting oftetraacetylethylenediamine (TAED), NOBS, isoNOBS,carbonylbiscaprolactam, benzoylcaprolactam, bis(2-propylimino)carbonate, bis(cyclohexylimino) carbonate, acetone O-benzoyloxime,anthranil, phenylanthranil, N-methylmorpholinoacetonitrile,N-methylpiperazine-N,N'-diacetonitrile and N-octanoylcaprolactam (OCL),and (c) more than 0.1 to less than 1.0% by weight of secondary amines asdefined in claim
 1. 9. A bleach or textile detergent composition,comprising:(a) 0.5-40% by weight of at least one bleach selected fromthe group consisting of sodium perforates, sodium carbonate perhydrates,C_(1-C) ₁₂ -percarboxylic acids, C₈ -C₁₆ -dipercarboxylic acids,imidopercaproic acids and aryldipercaproic acids, (b) 0-20% by weight ofbleach activators and (c) more than 0.1 to less than 1.0% by weight ofsecondary amines as defined in claim
 1. 10. A bleach or textiledetergent composition, comprising:(a) 0.5-40% by weight of bleach in theform of peroxy compounds and/or percarboxylic acids, (b) 0-20% by weightof bleach activators, and (c) 0.1 to less than 0.5% by weight ofsecondary amines as defined in claim
 1. 11. A bleach or textiledetergent composition, comprising:(a) 0.5-40% by weight of bleach in theform of peroxy compounds and/or percarboxylic acids, (b) 0-20% by weightof bleach activators, and (c) 0.01-5 of secondary amines as defined inclaim 1.